Spectroscopic studies of the intracluster hydration reaction of NO2 +

Yibin Cao, Jong-Ho Choi, Bernd Michael Haas, Mitchio Okumura

Research output: Contribution to journalArticle

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Abstract

Infrared spectra of NO2 +(H2O)n clusters formed in a pulsed discharge source were recorded by vibrational predissociation spectroscopy as a function of cluster size. A significant change in the vibrational spectra and the predissociation product yields were observed at n = 4, suggesting the onset of a rearrangement at this critical cluster size. For NO2 +(H2O)n with n ≤ 3, the clusters possessed red-shifted H2O bands and dissociated primarily by loss of H2O. These were clusters of H2O ligands bound to a nitronium ion core. At n = 4, we found evidence for the occurrence of an intracluster hydration reaction NO2 + + 2H2O → HNO3 + H3O+. Vibrational excitation of the cluster led to loss of HNO3 as the major channel, as well as loss of H2O. New vibrational bands appeared and were assigned to solvated H3O+ and to HNO3 ligands. With the H3O+ replacing NO2 + as the charge center, the clusters rearranged to form H3O+(H2O)2(HNO3). Upon addition of a fifth water molecule, the hydronium ion was further stabilized by completion of the first hydration shell, leaving HNO3 in the second shell.

Original languageEnglish
Pages (from-to)12176-12185
Number of pages10
JournalJournal of Physical Chemistry®
Volume98
Issue number47
Publication statusPublished - 1994 Dec 1
Externally publishedYes

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Hydration
hydration
Ligands
Vibrational spectroscopy
Ions
Vibrational spectra
Infrared radiation
Molecules
hydronium ions
Water
ligands
vibrational spectra
infrared spectra
occurrences
products
water
spectroscopy
excitation
molecules
ions

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Spectroscopic studies of the intracluster hydration reaction of NO2 + . / Cao, Yibin; Choi, Jong-Ho; Haas, Bernd Michael; Okumura, Mitchio.

In: Journal of Physical Chemistry®, Vol. 98, No. 47, 01.12.1994, p. 12176-12185.

Research output: Contribution to journalArticle

Cao, Y, Choi, J-H, Haas, BM & Okumura, M 1994, 'Spectroscopic studies of the intracluster hydration reaction of NO2 + ', Journal of Physical Chemistry®, vol. 98, no. 47, pp. 12176-12185.
Cao, Yibin ; Choi, Jong-Ho ; Haas, Bernd Michael ; Okumura, Mitchio. / Spectroscopic studies of the intracluster hydration reaction of NO2 + In: Journal of Physical Chemistry®. 1994 ; Vol. 98, No. 47. pp. 12176-12185.
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AB - Infrared spectra of NO2 +(H2O)n clusters formed in a pulsed discharge source were recorded by vibrational predissociation spectroscopy as a function of cluster size. A significant change in the vibrational spectra and the predissociation product yields were observed at n = 4, suggesting the onset of a rearrangement at this critical cluster size. For NO2 +(H2O)n with n ≤ 3, the clusters possessed red-shifted H2O bands and dissociated primarily by loss of H2O. These were clusters of H2O ligands bound to a nitronium ion core. At n = 4, we found evidence for the occurrence of an intracluster hydration reaction NO2 + + 2H2O → HNO3 + H3O+. Vibrational excitation of the cluster led to loss of HNO3 as the major channel, as well as loss of H2O. New vibrational bands appeared and were assigned to solvated H3O+ and to HNO3 ligands. With the H3O+ replacing NO2 + as the charge center, the clusters rearranged to form H3O+(H2O)2(HNO3). Upon addition of a fifth water molecule, the hydronium ion was further stabilized by completion of the first hydration shell, leaving HNO3 in the second shell.

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